Herbicidal s-aryl arylamides as herbicides

ABSTRACT

S-aryl arylamides characterized by the following formula:   WHERE R1 is unsubstituted C6-C10 aryl or substituted C6-C14 aryl having one or more of the following groups situated anywhere along its aromatic nucleus or nuclei: halogen, cyano, nitro, amino, C1-C6 monoalkylamino, C2-C8 dialkylamino, C2-C6 alkylamido, C1-C6 alkoxy, C2-C4 alkenyl, and C2-C4 mono- and poly-haloalkenyl, etc.; X is one or more of the following: halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 mono- and polyhaloalkyl, amino, C1-C6 monoalkylamino, C2-C8 dialkylamino, nitro, cyano, etc.; m is 0-2; n is 0-4; R is hydrogen, C1-C3 hydrocarbyl, C1-C6 alkoxy, etc.; and R2 is H, C3-C6 cycloalkyl, and C1-C6 hydrocarbyl, optionally substituted by halogen, hydroxy, alkoxy, thioalkyl, etc., have been found to possess herbicidal activity.

[111 3,753,679 [451 Aug. 21, 1973 HERBICIDAL S-ARYL ARYLAMIDES ASHERBICIDES [75] Inventor: Gopal H. Singhal, Westfild, NJ.

[73] Assignee: Esso Research and Engineering Company, Linden, NJ.

[22] Filed: Jan. 4, 1971 [21] Appl. No.: 103,852

Related US. Application Data [62] Division of Ser. No. 726,567, May 3,1968, Pat. No.

Primary Examiner-James 0. Thomas, Jr. Attorney-Chasan and Sinnock andJohn Paul Corcoran [57] ABSTRACT S-aryl arylamides characterized by thefollowing formula:

where R, is unsubstituted C -C3 aryl or substituted C -C aryl having oneor more of the following groups situated anywhere along its aromaticnucleus or nuclei: halogen, cyano, nitro, amino, C -C monoalkylamino, C-C dialkylamino, C C alkylamido, C,-C alkoxy, C C alkenyl, and C -Cmonoand poly-haloalkenyl, etc.; X is one or more of the following:halogen, C,-C alkyl, C C, alkoxy, C,-C monoand polyhaloalkyl, amino, C-C monoalkylamino, C -C dialkylamino, nitro, cyano, etc.; m is 0-2; n is0-4; R is hydrogen, C -C hydrocarbyl, C -C alkoxy, etc.; and R, is H, C-C cycloalkyl, and C -C hydrocarbyl, optionally substituted by halogen,hydroxy, alkoxy, thioalkyl, etc., have been found to possess herbicidalactivity.

7 Claims, No Drawings HERBICIDAL S-ARYL ARYLAMIDES AS HERBICIDESCROSS-REFERENCE TO OTHER APPLICATIONS This application is a divisionalof an application filed May 3, 1968 bearing Ser. No. 726,567, in thename of Gopal H. Singhal and entitled Herbicidal S-Aryl Arylamides, nowU.S. Pat. No. 3,576,872.

PRIOR ART l 0 DESCRIPTION OF THE INVENTION This invention relates tonovel S-aryl arylamides and their use as pesticides. More particularly,this invention relates to novel S-aryl aniline or anilidederivatives andtheir use as pesticides, preferably as herbicides.

In general, the S-aryl arylamides of this invention are characterized bythe formula:

R1S(O m where R is unsubstituted C, C aryl, a 5- or 6- 4o memberedheterocyclic compound having from I to 3 N-hetero atoms, or substitutedC C aryl having one or more of the following groups situated anywherealong its aromatic nucleus or nuclei: halogen, cyano, nitro, amino, C Cmonoalkylamino, C C, dialkylamino, C C alkylamido, C C alkoxy, aryloxy,thioalkyl, thioaryl, dialkylsulfamoyl, C C alkenyl, C C monoandpoly-haloalkenyl, etc.; X is halogen, C, C alkyl, C C alkoxy, C Cmonoand poly-haloalkyl, amino, C C monoalkylamino, C C dialkylamino,nitro, cyano, etc.; in is 0 2; n is 0 4; R is hydrogen, C, C,hydrocarbyl, C C, alkoxy, etc.; and R, is H, C, C cycloalkyl, andC Chydrocarbyl optionally substituted by halogen, hydroxy, alkoxy,thioalkyl, etc.

Such S-aryl arylamides can be prepared by a number of different,conventional methods. For example, in one method, denominated herebelowas Method A, these products can be prepared by reaction ofarylthioanilines of the general formula X R1S(O)m-@-1TIH w erein R X andR are as previously defined, with ac d anhydrides of the formula R beingas previously defined, either with or without a catalyst such aspyridine and in the presence or absence of a solvent.

Alternatively, the S-aryl arylamides of this invention can be preparedby another method, denominated herein as Method B, wherein:arylthioanilines, as de fined by (I), are reacted with an acid halide ofthe formula 'R COI-IaI (III) wherein R is as previously defined and Halis chlorine or bromine, preferably chlorine, the reaction being effectedin an inert solvent in the presence of an acid acceptor, such as anorganic or inorganic base.

Another preparative method that can be employed in this inventionisherein designated Method C, in which an arylthioaniline of (I) isreacted with an acid of the fonnula R CO H (IV),

wherein R is as previously defined, in the presence of a catalyst, suchas granulated .zinc metal.

Still another preparative method that can be employedherein is that ofMethod D, in which an arylthioaniline of (I) is reacted with an ester ofthe formula z z a wherein R, is aspreviouslydefined and R is loweralkylor aryl.

Finally, inMethod E, there is given still another preparative method bywhich the compounds of this. inventioncan be made. In this methodisocyanates derived from arylthioaniline (I) are reacted with carboxylicacids in accordance with the following equation:

wherein R k X and m are as previously defined.

Typical illustrative reactants employed for Method A include e.g.:

a. 4-(phenylthio)-3-chloroaniline with any of the following exemplaryanhydrides: propionic anhydride, acetic anhydride, Z-methyl-pentanoicanhydride, cyclopropane carboxylic anhydride, methacrylic acidanhydride,, isobutyric anhydride etc.;

b. 4-(p-chlorophenylthio)-3-ch.loroaniline with any of the anhydrides.given in (a);

c. 4-(3', 4-dichlorophenylthio)l-3-chloroaniline with any of theanhydrides given in (a);

d. 4-( p-bromophenylthio )-3-ch.loroaniline with any of the anhydridesgiven in (a); and

e. 4-(p-chlorophenylthio)-3-methylaniline with any of the anhydridesgiven in (a).

The reaction of Method A, as previously noted, can

be carried out either with or without an inert (organic) solvent. Theinert organic solvent can be a hydrocarbon such as ligroin, benzene,toluene, etc.; ethers such as dioxane; chlorinated hydrocarbons such aschlorobenzene, carbon tetrachloride, perchloroethylene, etc.

A few drops of a tertiary amine such as pyridine can be used as acatalyst.

Although the anhydride can be used as a solvent and the excess recoveredfor subsequent use, it is usually best to utilize equimolar amounts ofboth reactants.

The reaction temperatures can vary over a wide range of from about C. tothe boiling point of the solvent (ca. 150C).

The reactants employed in Method B are the arylthio-anilines (l) andacid chlorides (Ill).

Typical illustrative reactants employed for Method B include, e.g.:

a. 4-(phenylthio)-3-chloroaniline with any of the following acidchlorides:

acetyl chloride, propionyl chloride, isobutyryl chloride, methacrylchloride, 2-methyl pentanoyl chloride, fluoroacetyl chloride,cyclopropane carboxylic acid chloride, etc.; b.4-(p-chlorophenylthio)-3-chloroaniline with any of the acid chloridesgiven in (a);

c. 4-(3',4'-dichlorophenylthio)-3-chloroaniline with any of the acidchlorides given in (a);

d. 4-(p-bromophenylthio)-3-chloroaniline with any of the acid chloridesgiven in (a); and

e. 4-(p-chlorophenylthio)-3-methylaniline with any of the acid chloridesgiven in (a).

Equimolar ratios of the reactants are desirable in the reaction ofMethod B, and as solvents conventional solvents can be used: e.g.,hydrocarbons like ligroin, benzene, toluene, etc., ethers such asdiethylether, tetrahydrofuran, etc., chlorinated hydrocarbons such aschloroform, carbon tetrachloride, perchloroethyiene, etc. As acidacceptors organic bases such as pyridine, triethylamine, etc. orinorganic bases such as sodium or potassium carbonate can be used. It ispossible, moreover, to use an organic base such as pyridine as solventalso.

Typical illustrative reactants employed for Method C include, e.g.,4-(phenylthio)-3-chloroaniline; 4-(pchlorophenylthio)-3-chloroaniline;4-( bromophenylthio)-3-chloroaniline; 4-( 3 4'-dichlorophenylthio)-3-chloroaniline; 4-(pchlorophenylthio)-3-methylaniline, etc.; with anyof the following exemplary acids: propionic acid; 2- methylpentanoicacid; cyclopropane carboxylic acid; methacrylic acid, etc.

In this method, equimolar amounts of the aniline and the acid can beused, but an aniline/acid molar ratio of l to 2 is advantageous. Use ofa catalytic amount of zinc is also preferred. In addition, solvents suchas benzene, toluene, xylene, chlorobenzene, dichlorobenzene, etc. aresuitable for this reaction, along with a reflux time of 30 minutes to 24hours, preferably 2 to 6 hours.

Typical illustrative reactants employed for Method D include, e.g.:

4-(phenylthio)-3-chloroaniline; 4-(pchlorophenylthio )-3 -chloroaniline;4-( 3 ,4'- dichlorophenylthio)-3-chloroaniline;4-(pbromophenylthio)-3-chloroaniline;4-(pchlorophenylthio)-3-methylaniline, etc., with any of the followingexemplary esters: methyl propionate; methyl methacrylate; methylisobutyrate; methyl-2- methylpentanoate; methyl cyclopropyl carboxylicacid ester; etc.

The reaction occurring in Method D can be carried out by refluxingequimolar amounts of the reactants in an inert organic solvent such aschlorobenzene, dichlorobenzene, xylene, etc. Alternatively, however, theester can be used as a solvent, and the mixture refluxed until 1 mole ofthe alcohol is fractionated off from the products.

Typical illustrative reactants employed for Method E include, e.g.:

4-(phenylthio)-3-chlorophenyl isocyanate;4-(pchlorophenylthio)-3-chlorophenylisocyanate; 4-(3,4-dichlorophenylthio)-3-chl0rophenyl isocyanate;4-(pbromophenylthio)-3-chlorophenylisocyanate;4-(pchlorophenylthio)-3-methyl'phenylisocyanate; etc.; with any of thefollowing exemplary acids: propionic acid; Z-methylpentanoic acid;methacrylic acid; 2- methylpentanoic acid; fluoroacetic acid;cyclopropanecarboxylic acid; etc.

The reaction of Method E is carried out by refluxing the reactants in ahigh boiling, inert solvent such as toluene, xylene, chlorobenzene, ordichlorobenzene, e.g., until the evolution of carbon dioxide iscomplete.

The preferred, novel S-aryl arylamide compounds of this invention arecharacterized by the formula:

where:

l. R, represents unsubstituted C C, aryl such as phenyl, naphthyl, etc.;C C substituted aryl such as substituted phenyl, substituted naphthyl,etc., whose substituents can include one or more of the following:halogen; C, C alkoxy such as methoxy, ethoxy, npropoxy, isopropoxy;cyano; nitro; amino; C C alkylamido such as ethylamido throughhexylamido; C C, alkenyl such as ethenyl through butenyl; C C, monoandpoly-haloalkenyl such as fluoroethenyl, chloroethenyl,trifluoropropenyl, dibromobutenyl, etc.;

ll. X represents one or more of the following or combinations thereof:halogen such as fluorine, chlorine, bromine, iodine, preferablychlorine; C, C, alkyl, such as methyl through hexyl; C, C, alkoxy suchas methoxy through hexoxy; C, C, monoand polyhaloalkyl such as mono-,di, and tri-fluorochloro-, bromo-, or iodo-substituted methyl throughhexyl groups; amino, nitro, cyano; etc.;

[11. n is 0 2;

IV. m is 0 2; and

V. R represents hydrogen, C, C, cycloalkyl and C, to C hydrocarbyl,optionally substituted by halogen, hydroxy, alkoxy, thioalkyl, etc.

Non-limiting, typical preferred S-aryl, arylamides of this inventionexemplary of compounds embraced by the previous general formula in pages2 to 3 include, but by no means exhaustively:

N-propionyl-(halophenylmercapto)aniline; N-propionyl-(cyanophenylmercapto) aniline; N-propionyl-(nitrophenylmercapto) aniline; N-propionyl-(aminophenylmercapto)-aniline; N-propionyl- (substituted aminophenylmercapto) aniline; N- propionyl-(perhaloalkylphenylmercapto)aniline; N- propionyl-(alkylphenylmercapto) aniline; N-propionyl-(carboxyphenylmercapto) aniline: N-methacryl-(halophcnylmercapto)aniline; N-methacryl-(cyanophenylmcrcapto)aniline;N-mcthacryl-(nitrophenylmercapto)aniline;N-methacryl-(aminophenylmercapto)aniline;N-methacryi-(perhaloalkylmercapto)aniline; N-

methacryl-(alkylphenylmercapto)aniline; N-methacryl-(carbalkoxyphenylmercapto)aniline; N-2-methylpentanoyl-(halophenylmercapto)aniline; N-2-methylpentanoyl-(cyanophenylmercapto)aniline; N-2-methylpentan0yl-(nitrophenylmercapto)-aniline; N-2-methylpentanoyHaminophenylmercapto)aniline; N-Z-methylpentanoyl-(perhaloaikylphenylmercapto)aniline;N-2-methylpentanoyl-(alkylphenylrnercapto)aniline;N-2-methylpentanoyl-(carbalkoxyphenylmercapto)aniline;N-cycloproplonyl-(halophenylmercapto)aniline;N-cyclopropionyl-(cyanophenylmercapto )aniline; N-cyclopropionyl-(nitrophenylmercapto )aniline; N-cyclopropionyl-(aminophenylmercapto)aniline;N-cyclopropionyl-(perhaloalltylphenylmercapto)aniline;N-cyclopropionyl-(alkylphenylmercapto)- aniline;N-cyclopropionyl-(carbalkoxylphenylmercapto) aniline;N-alkyl-(halophenylmercapto)aniline;N-alkyl-(cyanophenylmercapto)-aniline; N-alkyl-(nitrophenylmercapto)aniline; Nall yl-(aminophenylmercapto)aniline;N-alkyl-(perhaloalkylphenylmercapto)aniline;N-alkyl-(alkylphenylmercapto)aniline;N-alkyl-(carbalkoxyphenylrnercapto)aniline;

Npropionyl-(halosubstituted phenylmercapto)- aniline;N-propionyl-(cyanosubstituted phenylmercapto)aniline;N-propionyl-(nitrosubstituted phenylmercapto)aniline;N-propionyl-(aminosubstituted phenylmercapto)aniline;N-propionyl-(perhaloalkylsubstituted phenylmercapto)aniline;N-propionyl-(alkylsubstituted phenylmercapto)aniline; N-propionyl-(carbalkoxy substituted phenylmercapto)aniline;N-methacryl-(halosubstituted phenylmercapto)aniline;N-methacryl-(cyanosubstituted phenylmercapto)- aniline;N-methacryl-(nitrosubstitued phenylmercapto)aniline;N-methacryl-(aminosubstituted phenylmercapto)aniline;N-methacryl-(perhaloalkylsubstituted phenylmercapto)aniline;N-methacryl-(alkylsubstituted phenylmercapto)aniline; N-methacryl-(carbalkoxysubstituted phenylmercapto)aniline; N-2-methylpentanoyl-(halosubstituted phenylmercapto )aniline;N-2-methylpentanoyl-( cyanosubstituted phenylmercapto)aniline;N-Z-methylpentanoyl- (nitrosubstituted phenylmercapto)aniline; N-Z-methylpentanoyl-(aminosubstituted phenylmercapto)aniline;N-2-methylpentanoyl-(perhaloalkylsub stituted phenylmercapto)aniline;N-2' methylpentanoyl-(alkylsubstituted phenylmercapto)aniline;N-Z-methylpentanoyl-(carballtoxy substituted phenylmercapto)aniline;N-cyclopropionyl- (halosubstituted phenylmercapto)aniline; N-cycIopropionyl-(cyanosubstituted phenylmercapto)aniline;N-cyclopropionyl-(nitrosubstituted phenylmercapto)aniline;N-cyclopropionyl-(aminosubstituted phenylmercapto)aniline;N-cyclopropionyl- (perhaloalkylsubstituted phenylmercapto)aniline; N-cyclopropionyl-(alkylsubstituted phenylmercapto)aniline;N-cyclopropionyl-(carbalkoxysubstituted phenylmercapto )aniline;N-alkyl-( halosubstituted phenylmercapto)aniline;N-alkyl-(cyanosubstituted phenylmercapto)-aniline;N-alkyl-(nitrosubstituted phenylmercapto)aniline;N-alkyl-(aminosubstituted phenylmercapto)aniline;N-alkyl-(perhaloalkylsubstituted phenylmercapto)aniline;N-alkyl-(alkylsubstituted phenylmercapto)aniline;N-alkyl-(carbalkoxylsubstituted phenylmercapto)aniline.

All of the foregoing specifically named examples of the compounds ofthis invention can, of course, be substituted by one or more of thedesired groups previously defined by R, R X, S, S0 or S0 For example,the alkyl, propionyl, methacryl, Z-methylpentanoyl, cyclopropionyl, andaniline moieties can be substituted by one or more of the exemplarygroups previously defined by R, R,, X, S, S0, or 80,.

Non-limiting, representative examples of the forego' ing preferredS-aryl arylamide compounds include, but by no means exhaustively:N-propionyl; N-methacryl; N-Z-methylpentanoyl; N-cyclopr-opionyl; formsof -(3- chloro, 4-phenyl or substituted phenylmercapto)aniline;(3-bromo, 4-phenyl or substituted phenylmercapto)aniline; -(3-cyano,4-phenyl or substituted phenylmercapto)aniline; -(3-nitro, 4-phenyl orsubstituted phenylmercapto)aniline; -(3-amino, 4-phenyl or substitutedphenylmercapto)aniline; -(3-perhaloalkyl, 4- phenyl or substitutedphenylmercapto)aniline; -(3- carbalkoxy, 4-phenyl or substitutedphenylmercapto)aniline.

The most preferred compounds of this invention include:N-propionyl-(3-chloro, 4-phenylthio)aniline; N-propionyl-(El-chloro,4-substituted phenylthio)aniline; N-propionyl-[ 3-chloro, 4-(3,4'-dichlorophenylthio)] aniline; N-propionyl-(3-chloro,4-phenylsulfonyl)aniline; N-propionyl-(3-chloro, 4- substitutedphenylsulfonyl)aniline; N-methacryl-(B- chloro, 4-phenylthio)aniline;N-methacryl-(3-chloro, 4-substituted phenylthio)aniline; Nmethacryl(3-chloro, 4phenylsulfonyl)-aniline; N-methacryl-(3- chloro, 4-substitutedphenylsulfenyl)-aniline; and the N-cyclopropionyl andN-Z-methyl-pentanoyl forms of: respectively, -(3-chloro,4-phenylthio)aniline; -(3- chloro, 4-substituted phenylthi|o)aniline;-(3-chloro, 4-substituted phenylsulfonyl)aniline. By the expression4-substituted phenyl is of course meant that a substituted phenyl groupoccupies the 4 position" of the aniline nucleus.

While not intending to be bound or limited by any theory, it isnevertheless believed that the presence of a chloro atom in the3-position and/or a phenylmercapto group in the 4-position tend toimpart increased herbicidal activity to the overall S-aryl arylamidemoiety as a whole.

As previously noted, the S-aryl arylamides of this invention are usefulas pesticides, particularly as herbi cides. When used as herbicides, thebiologically active S-aryl arylamides are preferably formulated with asuitable carrier or diluent or combinations thereof.

The term carrier" or diluent as used herein means a material, which canbe inorganic or organic and synthetic or of natural origin,-with whichthe active S-aryl arylamide is mixed or formulated to facilitate itsstorage, transport, and handling, and application. The carrier ispreferably biologically and chemically inert and, as used, can be asolid or fluid. When solid carriers are used, they are preferablyparticulate, granular, or pelleted; however, other shapes and sizes ofsolid carrier can be employed as well. Such preferable solid car rierscan be natural occurring minerals-although subsequently subjected togrinding, sieving, purification, and/or other treatments-including, forexample, ,gypsum; tripolite; diatomaceous earth; mineral silicates suchas mica, vermiculite, talc, and pyrophyllite; clays ol'themontmorillonite, kuolinite, or nttapulgite groups; calcium or magnesiumlimes; or calcite and dolomite, etc. (nrriers produced synthetically, asfor example, synthetic hydrated silica oxides and synthetic calciumsilicates can also be used, and many proprietary products of this typeare available commercially. The carrier can also be an elementalsubstance such as sulfur or carbon, preferably on activated carbon. Ifthe carrier possesses intrinsic catalytic activity such that it woulddecompose the active ingredient, it is advantageous to incorporate astabilizing agent, as for example, polyglycols such as diethylene glycolto neutralize this activity and thereby prevent possible decompositionof the S- aryl arylamides.

For some purposes, a resinous or waxy carrier can be used, preferablyone'which is solvent soluble or thermoplastic, including fusible.Examples of such carriers are natural or synthetic resins such as acoumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride,styrene polymers and copolymers, a solid grade of polychlorophenol suchas is available under the registered trademark Aroclor," a bitumen, anasphaltite, a wax, for example beeswax or a mineral wax such as paraffinwax or montan wax, or a chlorinated mineral wax, or a microcrystallinewax such as those available under the registered trademark Mikrovanwax." Compositions comprising such resinous or waxy carriers arepreferably in granular or pelleted form.

Fluid carriers can be liquids, as for example water, or an organicfluid, including a liquefied normally vaporous or gaseous material, or avaporous or gaseous material, and can be solvents or non-solvents forthe active material. For example, the horticultural petroleum spray oilsboiling in the range of from about 275 to about 575F., or boiling in therange of about 575 to about 1,000F. and having an unsulfonatable residueof at least about 75 percent and preferably of at least about 90percent, or mixtures of these two types of oil, are particularlysuitable liquid carriers.

For application as a soil-applied herbicide, the preferable carriershould be a granular inert carrier for example 25/50 mesh (U.S. sievesize) or can also be a simple or compound fertilizer which can be asolid, preferably granular or pelleted, or a liquid, as for example anaqueous solution in which the toxicant is suspended or emulsified.

The carrier can be mixed or formulated with the active material duringits manufacture or at any stage subsequently. The carrier can be mixedor formulated with the active material in any proportion depending onthe nature of the carrier. One or more carriers, moreover, can be usedin combination.

The compositions of this invention can be concentrates, suitable forstorage or transport and containing, for example, from about to about 90percent by weight of the active S-aryl arylamides, preferably from about20 to about 80 wt. percent. These concentrates can be diluted with thesame or different carrier to a concentration suitable for application.The compositions of this invention can also be dilute compositionssuitable for application. In general, concentrations of about 0.1 toabout 10 percent by weight, of active material based on the total weightof the composition are satisfactory, although lower and higherconcentrations can be applied if necessary.

The compositions of the invention can be formulated as wettable powderscomprising a major proportion of the S-aryl arylamide mixed with adispersing, i.e., delloceulatting or suspending, agent, and, if desired,a finely divided solid carrier and/or a wetting agent. This can be inparticulate form or adsorbed on the carrier and preferably constitutesat least about l0 percent, more preferably at least about 25 percent, byweight of the composition. The concentration of the dispersing agentshould in general be between about 0.5 and about 5 percent by weight ofthe total composition, although larger or smaller amounts can be used ifdesired.

The dispersing agent used in the composition of this invention can beany substance having definite dispersing, i.e., deflocculating orsuspending, properties as distinct from wetting properties, althoughthese substances can also possess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids suchas gelatin, glue, casein, gums, or a synthetic polymeric material suchas polyvinyl alcohol and methyl cellulose. Preferably, however, thedispersants or dispersing agents used as sodium or calcium salts of highmolecular weight sulfonic acids, as for example the sodium or calciumsalts of lignin sulfonic acids derived from sulfite cellulose wasteliquors. The calcium or sodium salts of condensed aryl sulfonic acid,for example, the products known as Tamol 731," are also suitable.

The wetting agents used can be non-ionic type surfactants, as forexample, the condensation products of fatty acids containing at least12, preferably 16 to 20, carbon atoms in the molecule, or abietic acidor naphthenic acid obtained in the refining of petroleum lubricating oilfractions with alkylene oxides such as ethylene oxide or propyleneoxide, or with both ehtylene oxide and propylene oxide, as, for example,the condensation product of oleic acid and ethylene oxide containingabout 6 to 15 ethylene oxide units in the molecule. Other non-ionicwetting agents like polyalkylene oxide polymers, commercially known asPluronics" can be used. Partial esters of the above acids withpolyhydric alcohols such as glycerol, polyglycerol, sorbitol, ormannitol can also be used.

Suitable anionic wetting agents include the alkali metal salts,preferably sodium salts, of sulfuric acid esters or sulfonic acidscontaining at least 10 carbon atoms in a molecule, for example, thesodium secondary alkyl sulfates, dialkyl sodium sulfosuccinate availableunder the registered trademark Aerosol, sodium salts of sulfonatedcaster oil, sodium dodecyl benzene sulfonate, etc. The resultingwettable powder should preferably be ground to an average particle sizeof about 2 20 microns.

Granulated or pelleted compositions comprising a suitable carrier havingthe active S-aryl arylamides incorporated therein are also included inthis invention. These can be prepared by impregnating a granular carrierwith a solution of the S-aryl arylamides or by granulating a mixture ofa finely divided solid carrier and the active S-aryl arylamides. Thecarrier used can consist of or contain a fertilizer or fertilizermixture, as for example, a superphosphate.

The compositions of this invention can also be formulated as solutionsof the active S-aryl arylamide ingredient in an organic solvent ormixture of solvents: for example alcohols; ketones, especially acetone;etc.

Compositions of the present invention can also be formulated asemulsifiable concentrates which are concentrated solutions ordispersions of the active ingredient in an organic liquid, preferably awater-insoluble organic liquid, containing an added emulsifying agent.These concentrates can also contain a proportion of water, for example,up to about 50 percent by volume,

, based on the total composition, to facilitate subsequent dilution withwater. Suitable organic liquids include, e.g., the above petroleumhydrocarbon fractions previously described.

The emulsifying agent can be of the type producing water-in-oil typeemulsions which are suitable for application by low volume spraying, oran emulsifier of the The present invention is further illustrated ingreater A solution of 3,4dichloro-l-nitrobenzene in 1.2 liters ofp-dioxane was made in a 4-necked 5 liter flask equipped with amechanical stirrer, a reflux condenser, a thermometer, and a droppingfunnel. To the solution was added a solution 289 g. ofp-chlorothiophenol and 84 g. of sodium hydroxide in 800 ml. of water and500 ml. of ethanol at a rapid rate. The reaction was exothermic and thetemperature increased to 50C. Within a few minutes the product startedseparating. The mixture was refluxed for minutes, allowed to cool toroom temperature, and wasdilu ted with 2 liters of water. The solidproduct was collected by filtration, washed well with water, and airdried. The yield of almost pureproduct was 98%, and the product had amelting point range of l2l-l22C. The resulting.arylmercapto-nitrobenzene can be recrystallized from a suitable organicsolvent, with consequent yields usually in the range of 90-lO0%.

The following Table, Table I includes a list of the compounds thusprepared:

'7 7 TABLE I Product Thiophenol reactant Nitrobcnzene reactant Productm.p., C. Thiophenol 3,4-dichloronitrobenzene 111-112 S- -N Ozp-Chlorothiophenol .do USE-123 (31- S--- --N Oz Dochloro-3-nitrobenzotrifiuoride 107-103 C l- S- C F:

l N 02 p-Toluenethiol 3,4-dlchloronitrobenzene 120-12? Ha C S- N O:

p-Chlorothiophenol 4-bromonitrobenzene 83-8 Cl S- N O:

3,4-dlch1orobenzenethiol. 3,4-dlch1oronitrobenzene. 129430 detail by thefollowing examples, but it is to be understood that the presentinvention, in its broadest aspects,

is not necessarily limited in terms of the reactants, or

In this example, a laboratory procedure is set forth for the preparationof a typical sulfur-containing nitro precursor,arylmercaptonitrobenzene.

Preparation of arylmercaptonitrobenzene EXAMPLE 2 In this example, thearylmercaptonitrobenzenes prepared in Example 1 were subjected to anoxidation step to conver their sulfide content to sulfone. Anexperimental procedure for this step is described below, wherein thespecific preparation of 4-phenylsulfonyl-3- chloro-nitrobenzene is setforth:

Preparation of 4-phenylsulfonyl-3-chloronitrobenzene A stirredsuspension of 43.l grams of 4-phenylmercapto-3-chloronitrobenzene in 850ml. of glacial acetic acid was heated to a temperature of 60C. and asolution of 40 grams of potassium permanganate in 450 ml. of water wasthen added in portions at such a rate that temperature of the reactionwas maintained at C. without external heating. The mixture was stirredfor 1 hour. Sodium bisulfite was added to decompose the oxidizingagents; and to the mixture 2 kg. of crushed ice were added. The whitesolid product was collected, washed with water, and air dried. The yieldof the resultant product was 40.5 g. (84 percent), and had a meltingpoint range of l4l-l43C.

Other sulfides can be oxidized by the same method or with an excess of30 percent hydrogen peroxide.

EXAMPLE 3 Reduction of the nitro group of the previously preparedsulforie of Example 2 or of the sulfide of Example 1 was effected inthis example. Specifically, the preparation of4-chlorophenylmercapto-3-chloroaniline is described in the followingprocedure to illustrate this reduction step. Preparation chloroanilineTo a stirred suspension of (1) 400 grams of 4-chlorophenylmercapto-3-chloronitrobenzene, (2) 800 grams of iron powderand (3) 2 liters of water at 50C. were added dropwise 50 ml ofconcentrated hydrochloric acid. After the reaction subsided, the mixturewas refluxed for 2.5 hours, chilled, treated with 45 g. of sodiumbicarbonate, and then filtered. The solid was extracted with 1.6 litersof boiling benzene in four portions.

The combined benzene solution was filtered and benzene removed underreduced pressure. The residual solid was washed with 500 ml. ofpetroleum ether to give 329 g. (91.4 percent) of the product, which hada melting point range of 70 71C.

Alternatively, the nitro compounds can be easily reduced equally well byusing iron-acetic acid, zincacetic acid, or tin-hydrochloric acid, orcatalytically in of 4-Chlorophenylmercapto-3- I a conventional manner.

Table 11 includes a list of the compounds thus prepared.

EXAMPLE 4 From the recovered aromatic amine, a number of exemplaryS-aryl, arylamides of this invention can be prepared in accordance withthe following exemplary syntheses, showing the preparation ofN-[4-(pchlorophenylthio)phenyl] propionamide and of N-[4-(p-phenylsulfonyl)-3-chlorophenyl]-2-methyl pentanamide.'

Preparation of N-[4-(p-chlorophenylthio)phenyl] propionamide A stirredmixture of 9.5 grams of p-chlorophenylmercaptoaniline, 5.5 grams ofpropionic anhydridc, ml. of benzene and a few drops of pyridine wasrefluxed for 2.5 hours. The mixture was diluted with petroleum etheruntil turbidity appeared, at which time the mixture was allowed tostand. The resulting solid was collected and dried, affording a yield of1 1 g. (93 percent) of the product having a melting point rang ofl45146C.

Preparation of N-[4-(p-Phenylsulfonyl)-3-chlorophenyll-2-methylpentanamide To a stirred solution of 8 grams of 4-phenylsulfonyl-3-chloroaniline in 100 ml. of pyridine was added dropwise 5.5 grams of2-methylpentanoyl chloride. The mixture was heated at 75-80C. for 3hours, cooled to room temperature, and poured into a solution of gramsof concentrated hydrochloric acid in 700 grams of water. The oil whichseparated out was taken up in benzene, washed successively with 10percent hydrochloric acid, water, and a 5 percent sodium bicarbonatesolution, dried over calcium chloride, filtered; and the solvent wasthen removed. The residual oil on treatment with ether-petroleum ethergave 8.3 grams (75.4 percent) of the solid product having a meltingpoint range of ll2-l 14C.

Table Ill includes a list of other arylamides thus prepared.

TABLE III Arylamlde product M.P., C.

0 171172 Q s OQNHii 01m 0 (In CgHs JG-98 cr-Q s NHCCH-C;H1

N HC 0 H;

O 132133 cm-Q-s NHC CIHI Cl EXAMPLE 5 As an alternative procedure,S-aryl arylamide compounds such as N-[4-(phenylthio)-3-chlorophenyl1cyclopropane carboxamide can be prepared according to and 200 ml. ofpetroleum ether were added, and the resulting mixture was stirred for afew minutes. The resulting solid which formed was collected, washed withwater, and then dried, to yield 11.6 g. (74.5 percent) of the productwhich had a melting point range of 154-l55C.

Exemplary of arylamides that were prepared by this method are thoseincluded in Table IV below.

TABLE IV TAB LE IV 'onitinuctl Arylamldo product EXAMPLE 6 In thisexample, the preparation of4-p-chlorophenylmercapto-3-chlorophenylisocyanate is described.Preparation of 4-p-chlorophenylmercapt0-3- chlorophenylisocyanate To astirred solution of 40 grams of phosgene in 400 ml. of toluene wasadded, dropwise at 20-30C., a solution of 67.5 grams of4-p-chlorophenylmercapto-3- chloroaniline in 300 ml. of toluene. Therewas an immediate precipitation of a solid. The mixture was cautiouslyheated with stirring during 1 hour to 95C. and finally refluxed for 2hours. Toluene was distilled off. The residual oil was extracted with600 ml. of boiling hexane in three portions." The hexane solution oncooling gave 57 grams (72.5 percent) yield of the product,

which had a melting point range of 75-77C. Arylsmlde product Otherisocyanates can be prepared essentially by the same method, and toluenecan be replaced by other -s--uno cm .cm solvents such as dioxane, ethylacetate, etc.

.5 p 4 EXAMPLE 7 i o Representative S-aryl arylamide compounds fromthose prepared in the previous examples were evalu- 01 ated forherbicidal activity in this example.

0-1 Post-emergence herbicide tests were carried out by 0 4455s sprayingthe materials as aqueous solutions or very l small particle aqueoussuspensions onto the test plants which were at the l to 2 leaf stage ofgrowth. Sprayers 1 r A were calibrated to deliver a certain volume ofliquid, 0 1814820 and the calculated amount of active ingredient which 140 would give a rate corresponding to the indicated CITQSTQTNHC poundsper acre (broadcast) was dissolved or sus- X pended. The plants wereheld in the greenhouse for 7 to 14 days before herbicide ratings weremade. 21141 A Rating system of 0-10 was used to score the tests.Cl-Q-S-Q-NHC-Q-NO: The 0 to 10 scale is defined as: 0 no injury; 1 3slight injury; 4 6 moderate injury, plants may die; 1 7 9 severe injury,plants will probably die; and 10 o Isl-182 all plants dead. m-Q --NH|C|Testing dataon the active compounds is found in Table V. The ratingsystem used is indicated for each o1 series "of tests.

TABLE v Dosa e rate it Morning Velvet IbJacre glory leaf Mustard CornOats Soybeans o 5 -10 to 10 4 s 5 CIS-NHC [i i8 3 i ii 0 a 10 1o, 10 9 s6 Q i 0. 63 10 10 1o 3 5 5 s 0 5 1o 9 1o 10 a s 0.63 10 9 10 2 o s TABLEV Continued Dose rate n Morning Velvet lbJacre glory leaf Mustard CornOats Soybeans O 10 V 10 2 3 ll 0. 63 2 9 9 2 1 S NHO-CHPr O: l

CH; Cl

01- 8- NBC\ CaHs wherein X is independently selected from the groupconsisting essentially of hydrogen, chlorine, bromine or CH and whereinR is C -C alkyl, chloro-substituted C -C alkyl, cyclopropyl ormethacryl; said composition being applied in an amount sufficient tocause deterioration of the vegetation.

2. A method according to claim 1 wherein said composition includes aparticulate siliceous carrier.

3. A method according to claim 1 wherein said compound is 4. A methodaccording to claim 1 wherein said compound is 5. A method according toclaim 1 wherein said compound is 6. A method according to claim 1wherein said compoundis 01-- -s NHC I. A method according to claim 1wherein said compound is

2. A method according to claim 1 wherein said composition includes aparticulate siliceous carrier.
 3. A method according to claim 1 whereinsaid compound is
 4. A method according to claim 1 wherein said compoundis
 5. A method according to claim 1 wherein said compound is
 6. A methodaccording to claim 1 wherein said compound is
 7. A method according toclaim 1 wherein said compound is